100,
98
c
I
I
1
I
I
I
I
1
A
.-6 1
e A x
92
o 90
I
1.8
1.9
2.0
2.1
I 22
I 2.3
I 2.4
Run Run Run Run
i 7
I
9
10 II
I
2.5
I 2.6
2.7
Acidulation ratio Figure 7.
Effect of acidulation ratio on conversion
six rods -were used instead of the 10 rods used in previous runs. A lower heating jacket temperature of 325’ F. was used instead of 350’ F. The drying air rate was increased from 0.365 cu. ft. per minute to 0.512 cu. ft. per minute, and the drying air temperature was decreased from about 160’ to 73’ F. The opposing effects of changes in these operating variables resulted in no distinguishable changes in the product, except for higher moisture and free acid content. This could be corrected either by increasing the temperature, increasing the residence time, increasing the amount of drying air or its temperature, or by decreasing the acid and rock feeding rates. Moisture content between 3 and 4% gave optimum results and satisfactory free acid contents. Figure 7 indicates the effect of the
Chemists, “Official Methods of Analysis,” Washington, D. C., 1950. (2) Berlin, L. E., Mikerov, V. A,, Zuchkoy, E. N., J . Chem. Ind. (Moscow) 5, 48-51 (1933); Chem. Abstr. 26, 1498 (1932). (3) Bridger. G. L., Tenn. Valley Authority, Chem. Eng.Rept. 5 , 1949. (4) Dragunov, S.S., Fertilizers and Crops IC‘.S.S.R.) 2. 409 (1930): Chem. Abstr. . 25, 2247 (1931). (5) Inskeep, G. C., Fort, R. I\-., lt’eber, W. C., Ind. Eng. Chem. 48, 1805 (1956). (6f Knox, W. H., Jr., U. S. Patent 2,160,700 (May 30, 1939). (7) Marshall, H. L., Rader L. F., Jacob, K. D., Ind. Eng. Chem. 25, 1253 (1933). (8) Martinez, F., 51. S. thesis, Iowa State Universiry, 1959. (9) Meyers, H. H., U. S. Patent 1,475,959 (1923). (10) Nunn. R . J.. Dee. T. P.. J . Sci. Food Agr. 5,257 (1954j. (11) Parrish, P., Ogilvie, -4.%“Calcium Superuhosuhate and ComDound Fertili‘zers,” i n d ed., Hutchikon’s Publications, London, 1946. (12) Phillips, A4.B., Young, R . D.: Lewis, J. S.,Jr., Heil, F. G., J. AGR. FOODCHEM.6, 584 (1958). (13) Rounsley, R. R . , Ph.D. thesis, Iowa State University, 1957. (14) Rounsley, R . R., Boylan, D . R., J. AGR.FOODCHEM.6, 677 (1958). (15) Sauchelli, V., “The Chemistry and Technology of Fertilizers,” Reinhold, Yew York, 1960. Receized f o r review Nouember 15, 1963. Accpppted .Wararch 12, 7964. Ditision of Soil m d Fertilizer Chemistry, 145th .Vleeting, ACS, 1Vez York, September 7963.
variation of the acidulation ratio on the conversion obtained in various runs. The particle size analysis of the rock used and the product triple superphosphate are given in Table V. Agglomeration of fine particles in the product of these runs prevented correct indication of the degree of grinding. A residence time in the mill of about 45 minutes was indicated during run 10 by introducing ground charcoal with the rock feed and subsequent examination of the product for color. The product was examined for storage characteristics after one month and two months. I t was found free flowing and had excellent physical condition.
Literature Cited (1) Association of Official Agricultural
_
~
G R O W T H REGULATOR RESIDUES
Determination of Beta-Hydroxyethylhydrazine in Pineapples
METHRATTA P. THOMAS and HENRY J. ACKERMANN Olin Research Center, Olin Mathieson Chemical Corp., N e w Haven 4, Conn.
A microanalytical method for the isolation and determination of beta-hydroxyethylhydrazine (HEH) in pineapples is described. The method consists of blending and extracting the HEH from the fruit with water. After the interfering pigments in the extract are removed with ion exchange resins, the HEH is reacted with cinnamaldehyde to produce a yellow color. The intensity of the color is proportional to the concentration of HEH, and is measured at 420 mp. The amount of HEH in the sample is then calculated from a standard curve.
I
of economic importance to the pineapple growers to be able to make their plants fruit uniformly, and a t a predetermined date. This can be achieved by spraying the plants with chemical agents which induce flowering and thus control the date of harvest ( 7 ) . One of the very promising chemicals in this respect is beta-hydroxyethylhydrazine (Omaflora, O h trade name) (3, 4, 6 ) . The method presented was T IS
432
A G R I C U L T U R A LA N D
developed to determine microgram quantities of Omaflora in the presence of pineapple.
Experimental Apparatus. The apparatus included chromatographic tubes with Teflon stopcocks, Waring Blendor, International chemical centrifuge, and Beckman Model B spectrophotometer. Reagents. DEIOSIZED LL‘ATER. DisFOOD CHEMISTRY
tilled water was deionized using Amberlite hIB-3 resin. DILUTEHCL. Prepared bv mixing 30 ml. of concentrated HCl and 7 0 ml. of deionized water. I O NEXCHANGE RESINS.Dowex 1-X8 and 5O\\‘-X8, 50- to 100-mesh, were used in the investigation. The Dowex 1 resin. obtained in the C1- form, \vas converted to the OH- form according to the procedure recommended by the
ards, a known quantity of H E H was manufacturer ( 2 ) . I t was found preferadded to the sample. The sample was able to remove the fines .from the resins, then blended with 100 ml. of deionized and also not to keep the OH- form of water in a \Varing Blendor. The blend Dowex 1 beyond 3 or 4 days. was then filtered and washed quantitaCISNAMALDEHYDE RE:AGENT.Pretively with deionized water, using a pared by mixing 95 ml. of denatured chemical centrifuge lined with a strip alcohol (formula 2B), 18.5 ml. of deionof Whatman No. 1 filter paper. T h e ized water, and 6 ml. of concentrated filtrate and the washings were collected HC1 in a brown bottle, cooling the mixin a 600-ml. beaker. ture to room temperature, and then addAbout 80 grams of the OH- resin ing 2 ml. of Eastman Grade transwere slurried with deionized water and cinnamaldehyde (Distillation Products poured into a 40 X 600-mm. chromatoIndustries, Rochester 3. K. Y.). T h e graphic tube which contained a plug of reagent was prepared fresh daily. glass wool and some water. T h e resin BETA - HYDROXYETHYLHYDRAZINE. was allowed to settle and then washed Olin Mathieson beta-hydroxyethylhydra\vith deionized water until the washings zine (HEH), refined grade, containing were neutral to “Hydrion” paper. 957%H E H , was used for the investigation 4 second 20 X 400-rnm. chromato(5). Solutions for the standard curve graphic column was prepared similarly, were prepared in dilute HCI, whereas using 20 grams of Dowex 5OTY. T h e those for the recovery standards were column was washed with dilute HCI until made in deionized water. the ivashings were visually colorless, and Preparation of Standard Curve. then rinsed \vith deionized water until About 0.1 gram of H E H was accurately the effluent \vas neutral. weighed into a 100-rnl. volumetric flask, The filtrate and the washings from and the solution was macle up to volume the centrifuge were passed quantitatively with dilute HC1. Appropriate aliquots through the OH-resin, and then through of this solution were diluted with dilute the H- resin column. T h e H + resin HC1 to prepare standards containing column !vas then Xvashed with deionized 0.1 to 2 pg. of H E H per 1111. From each water until the washings were neutral standard, 6-ml. aliquots were pipetted and colorless. A positive air pressure into 50-ml. volumetric flasks. Into each of about 10 inches of Hg was applied to flask, 18 ml. of the cinnamaldehyde the columns whenever necessary. The reagent were added and allowed to H E H under these conditions remained react for 30 minutes. A reagent blank on the H + resin. I t was then eluted was prepared by mixing 6 ml. of dilute with dilute HC1, and 100 ml. of the HCl and 18 ml. of the reagent. At the eluate were collected in a volumetric end of the reaction period, the absorbflask. The eluate was filtered through ances of the solutions viere measured a TVhatman No. 5 filter paper to remove a t 420 mp against the re,agent blank in the cloudiness. and 6 ml. of the filtrate 5-cm. cells. The absorbances were then were reacted with 18 ml. of reagent for 30 plotted against the conceritrations of the minutes. The absorbance of the solucorresponding standards to obtain the tion was then measured against a reagent standard curve. The slope of the line blank prepared as described previously. gave the absorbance due to 1 pg. of H E H T h e apparent H E H in the eluate was in 1 ml. of dilute HCI. Data for prepathen calculated using the slope of the ration of the standard curve are given in standard curve. A pineapple blank was Table I. determined b>- repeating the procedure Extraction, Isolation, and Determinawithout adding any H E H to the sample. tion of HEH. The pineapple was cut Consequently, the net recovery of H E H lengthwise through the center to obtain was calculated. pieces which contained representative amounts of shell, flesh, and core in relative proportions. About 200 grams of Results and Discussion the pieces were weighed and sliced into Solutions of H E H decompose gradusmall fragments. For recovery standally. Hence. they are prepared fresh daily. Acid solutions are more stable than the aqueous ones. Cinnamaldehyde and H E H react in acid medium to produce cinnamaldehyde Table I. Data for Standard Curve” hydrazone which, under the conditions HEH, used in the investigation, is stable for a t Solution p g . per MI. Absorbonce least 2 hours. 1 0.140 0.040 2 3 4 3
-6 8
0,474 0.790 1.320 1.580 2,050 2,370 2 370
Slope of the line = 0.30
0.145 0.240 0.400 0.480 0.620 0.720 0,722
CsHsCH=cCHCHO
+
H-
H?SNHCHzCHaOH -+ CpHe,CH=CH-CH=SNHCHzCHzOH
+ Ha0
The hydrazone solution has a maximum absorbance a t 390 mp. At this Lvavelength, the reagent used has a high back-
ground absorbance which is avoided by choosing 420 mp for the experimental measurements. The standard curvc sho\vs that the solutions at 420 mp obe).ed Beer’s Law. The ion exchange resins, when washed after standing for some time, give a yellow effluent. They are washed in the column as described in the text immediately before they are used. Fresh columns are prepared for each run. Recoveries are reproducible if rhc duration of analysis is kept consistent. Amounts as low as 0.015 p.p.m. H E H have been added to pineapples, and a n average of 79.4% recovery ha? been obtained (Table 11). In such c a w . the HCI eluate from the H + column is collected in 25-ml. fractions. The H E H is found in the second fraction. Blanks for such recoveries are run in a corresponding manner.
Table II. Blanks and Recovery Values Obtained with Whole Fresh Pineapples Recovery HEH -~ Added, Found,
Blanks,
P.P.M. HEH
p.p.m.
%
0,025 0.030 0,025 0.015 0.020 0.015 0.025 0.025 0.015 0.015
0.040 0.045 0.071 0.625 0.640 0.710 0.725 0.800 0.845 1.450 1.460
78 8 75.6 79.3 79.8
78.8 76.6 76.4 75.5 79.8 78.2 7 - .3
Acknowledgment IValter Carter and H. Y . Young of the Pineapple Research Institute or Ha\raii initiated and conducted field tests and preliminary investigations on the development of a method of analysis for H E H residues. Justin H . Reinhart and Sylvan I. Cohen. Pesticide Research Laboratories. Olin Mathieson Chemical Corp., New Brunswick, N. J., contributed their assistance and performed liaison Ivith personnel in Hawaii. Literature Cited (1) Collins. .J. L.. “The Pineapple.” pp. 152-4, Interscience, Neiv York, 1960. ( 2 ) “Dotvex: Ion Exchange.’‘ 11. S i . The Dow Chemical Co., Xlidland, Mich. (3) Golving, D. P.. Leeper, K . \ V . , Botan. Gar. 123, 34-43 (1961). (4) Gowing, D . P.. Leeper, R . T I - > Scietice 122, 1267 (1955). ( 3 ) Olin Mathieson Industrial Chemicals Division Bulletin on “Mathieson BHydroxyethylhydrazine.” (6) Olin Mathieson International Division Agricultural Bulletin. S o . 44. Rmiued for
rrziezv
June 18, 79h,?.
.Ifarch 9, 19ti 1.
VOL. 12, NO. 5, SEPT.-OCT.
1964
433
AccrpLd
